EP2096099A1 - Purification d'alcools fluores - Google Patents

Purification d'alcools fluores Download PDF

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Publication number
EP2096099A1
EP2096099A1 EP09156396A EP09156396A EP2096099A1 EP 2096099 A1 EP2096099 A1 EP 2096099A1 EP 09156396 A EP09156396 A EP 09156396A EP 09156396 A EP09156396 A EP 09156396A EP 2096099 A1 EP2096099 A1 EP 2096099A1
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EP
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Prior art keywords
water
iodo
perfluoroalkanoic
level
alcohols
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EP09156396A
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German (de)
English (en)
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EP2096099B1 (fr
Inventor
Alexander Borisovich Shtarov
Stephen James Getty
Axel Hans-Joachim Herzog
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/34—Halogenated alcohols
    • C07C31/38—Halogenated alcohols containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound

Definitions

  • This invention relates to a process for the purification of fluorinated alcohols.
  • Trace levels of perfluoroalkanoic acid impurities may occur in intermediates used in the manufacture of fluorinated alcohols. It is desirable to limit formation of these impurities in fluorinated intermediates and also during the manufacture of various polymer products using such intermediates. Furthermore, it is also desirable to eliminate or significantly reduce the occurrence in fluorinated intermediates and polymer products of potential perfluoroalkanoic acid precursors, such as their esters with 2-perfluoroalkylethyl alcohols, and perfluoroalkyliodides. Both these classes of compounds can be readily degraded by hydrolysis and/or oxidation to form perfluoroalkanoic acids.
  • Fluorinated alcohols are widely used as intermediates to prepare water and oil repellents, as well as soil and stain release compositions for both hard- and soft-surfaced substrates.
  • substrates include building materials, such as architectural stone and tile; textiles and fabrics from natural and synthetic fibers used in apparel and carpet; as well as other surfaces.
  • Fluorotelomer alcohols are a particular class of fluorinated alcohols used in these applications.
  • Fluorotelomer alcohols can be prepared industrially by multiple processes that include: telomerization of pentafluoroethyliodide with tetrafluoroethylene to yield perfluoralkyliodides F(CF 2 CF 2 ) n I; reaction of these perfluoroalkyliodides with ethylene to provide 1-iodo-1H,1H,2H,2H-perfluoroalkanes having the structure F(CF 2 CF 2 ) n CH 2 CH 2 I; followed by hydrolysis to yield 1H,1H,2H,2H-perfluoroalkan-1-ols, F(CF 2 CF 2 ) n CH 2 CH 2 OH.
  • Bladel et al. disclose a process for the recovery of highly fluorinated carboxylic acids useful as emulsifiers from fluoropolymer dispersions. Processes for the recovery of fluorinated acids from product streams do not destroy the fluorinated acids, and may leave a significant residue of the acid in the extracted liquid product.
  • Japan patent application 2003/267900 describes a process for the decomposition and removal of water-soluble fluorine-containing carboxylic acids, having the fluorocarbon chain interrupted by oxygen or nitrogen, when dissolved in water at temperatures of 200°C or less in 24 hr.
  • Perfluoroalkanoic acids especially their more thermally stable linear isomers
  • esters are substantially more stable under these reaction conditions and are relatively insoluble in water. This process would not selectively remove perfluoroalkanoic acids, their esters and perfluoroalkyliodide impurities from fluorinated alcohols.
  • the present invention provides such a process.
  • the present invention comprises a process for selectively reducing the level of perfluoroalkanoic acids or salts thereof, perfluoroalkanoic esters, and perfluoroalkyliodides in fluorinated alcohols comprising heating a fluorinated alcohol, or mixtures thereof, containing said acids, salts, esters, and/or iodides to a temperature of at least 175°C in the presence of water and at least one base additive.
  • the present invention further comprises a process for selectively reducing the level of perfluoroalkanoic acids and salts thereof in the presence of 1-iodo-1H,1H,2H,2H-perfluoroalkane comprising heating a 1-iodo-1H,1H,2H,2H-perfluoroalkane, or mixtures thereof, containing said perfluoroalkanoic acids or salts thereof to a temperature of at least 175°C in the presence of at least one organic additive.
  • the present invention further comprises the products prepared by each of the above processes.
  • (meth)acrylic and “(meth)acrylate” as used herein denote: acrylic and methacrylic; and acrylate and methacrylate, respectively.
  • fluorinated alcohols denotes compounds of the structure of Formula 1 or mixtures thereof: R f -(CH 2 ) m OH Formula 1 wherein m is 2 or 3, R f is a linear or branched C n F (2n+1) , and n ranges from 2 to about 20.
  • pertluoroalkyliodides denotes 1-iodoperfluoroalkanes of the structure of Formula 2 or mixtures thereof: R f -I Formula 2 wherein R f is as defined above.
  • fluorotelomer iodides denotes compounds of the structure of Formula 3 or mixtures thereof: R f -CH 2 -CH 2 -I Formula 3 wherein R f is as defined above.
  • the processes of the present invention significantly reduce the levels of specific perfluoroalkyl impurities in fluorinated alcohols.
  • These impurities include perfluoroalkanoic acids or salts thereof, perfluoroalkyliodides, and perfluoroalkanoic acid esters of fluorotelomer alcohols; and also perfluoroalkanoic acid esters of other alcohols used as processing aids, such as isopropyl alcohol.
  • the process of the present invention comprises thermal treatment of fluorinated alcohols, singly or in admixture, containing impurities as noted above at a temperature above about 175°C, in the presence of water and at least one base additive.
  • the thermal treatment is above about 185°C, and more preferably above about 195°C. Degradation of the impurities is slower at lower temperatures, and becomes less practical, especially below about 175°C.
  • the upper temperature for the thermal treatment is about 225°C and preferably about 215°C. Above this temperature range competing reactions may produce additional undesired impurities.
  • the thermal treatment is carried out in the presence of water and one or more base additives.
  • the thermal treatment is also carried out in the presence of a hydrogen atom donor.
  • Water is present in the thermal treatment, preferably in the total amount of from about 5% to about 50%, preferably from about 10% to about 20%, based on the weight of fluorotelomer alcohol being treated. While the hydrolysis proceeds in the presence of higher water concentrations, the reaction volume is increased without providing any advantage.
  • the water facilitates the hydrolysis and removal of perfluoroalkanoic acid esters and perfluoroalkyliodides. In certain cases, some water may be present in the fluorotelomer alcohol being treated, and this water content is included in calculations to determine the amount of any additional water needed for thermal treatment.
  • Base additives suitable for use in the practice of this invention are Br ⁇ nsted bases capable of forming a salt or complex with the perfluoroalkanoic acid, including but not limited to selections from the group consisting of ammonia and its common salts such as ammonium chloride; primary, secondary, and tertiary amines and their salts; alkali metal hydroxides; and alkali metal salts, such as carbonates, bicarbonates, and acetates; and mixtures thereof.
  • the most effective base additives are typically used at a level ranging from about 0.1 % to about 5% by weight, based on the weight of the fluorotelomer alcohol. A level ranging from about 0.1% to about 2% is preferred.
  • the fluorinated alcohol, water, one or more base additive, and optional hydrogen donor are mixed together and agitated during heating.
  • Minimizing side reactions that lead to color formation during the course of thermal treatment is an advantageous aspect for controlling the quality of the finished fluorotelomer alcohols.
  • the selection of base additive influences color formation. Color may be a result of the formation of conjugated by-products from nitrogen and sulfur compounds that are present in trace amounts. For instance, thermal treatment with ethanolamine or diethanolamine produces fluorotelomer alcohol having lighter color than does thermal treatment with stronger base such as ammonia.
  • At least one hydrogen atom donor in addition to the base itself, may also be employed during the thermal treatment. These hydrogen atom donors facilitate phase transfer between organic and aqueous phase, and promote decomposition of perfluoroalkyliodides.
  • Optional effective hydrogen donors are organic molecules containing electron-donating substituents. Preferred substituents include, but are not limited to amino-, alkoxy-, and alkyl-substituents. Suitable hydrogen atom donors are chosen from glycols, alkyl alcohols, ethers, acids, amines, salts thereof for each of the foregoing, and metal complexes thereof for each of the foregoing.
  • Optional hydrogen donors are typically used at from 0% to about 20%, preferably from 0% to about 10%, and most preferably from 0% to about 5% by weight, based on the weight of fluorotelomer alcohol or fluorotelomer iodide material being treated.
  • effective hydrogen atom donors include, but are not limited to glycols such as ethylene glycol, 1,2-propyleneglycol, di(ethylene glycol), tri(1,2-propylene glycol), and tetraglyme; alkyl alcohols, such as 2-propanol; alkylamines such as ethanolamine, diethanolamine, triethanolamine, diethylamine, diisopropanolamine, N-ethyl-N-ethanolamine and triethylamine, and the salts of these amines; ammonia and its salts, such as ammonium chloride.
  • glycols such as ethylene glycol, 1,2-propyleneglycol, di(ethylene glycol), tri(1,2-propylene glycol), and tetraglyme
  • alkyl alcohols such as 2-propanol
  • alkylamines such as ethanolamine, diethanolamine, triethanolamine, diethylamine, diisopropanolamine, N-ethyl-N-ethanolamine and
  • the base additives and optional one or more hydrogen atom donor additives are readily separated from the fluorinated alcohol by washing with water, or with water combined with dilute base or acid. Such aqueous extraction is followed by vacuum drying at about 0.5 to about 40 kPa at about 60°C to about 100°C. Residual levels of the base additives and of hydrogen atom donors contained in the isolated fluorotelomer alcohols are sufficiently low to have no detectable effect on product quality.
  • the process of the present invention is used to remove perfluoroalkanoic acids or salts thereof, perfluoroalkanoic acid esters, and perlluoroalkyliodide impurities from individual fluorinated alcohols or mixtures of their homologues.
  • the process of the present invention reduces the levels of C 2 -C 20 perfluoroalkyl impurities.
  • the alcohols are further used to make finished products such as polyurethanes, (meth)acrylates, phosphate esters, and other polymers.
  • perfluoroalkyl radicals and/or perfluoroalkyl radical-anions abstract hydrogen atoms from a donor to form 1H-perfluoroalkanes.
  • Perfluoroalkyl radicals are generated both by the decarboxylation of perfluoroalkanoic acids and/or salts thereof, and also by homolytic cleavage of the C-I bond of perfluoroalkyliodides.
  • Perfluoroalkyl radical-anions are formed from perfluoroalkyliodides by single electron transfer (SET) mechanisms.
  • the present invention minimizes Reaction 1 by careful selection of the treatment base reagent, such as alkylamines, ammonium or alkaline metal salts instead of alkaline metal hydroxides.
  • thermal treatment of fluorotelomer iodides, singly or in admixture, in the presence of at least one organic additive enables removal of perfluoroalkyliodides and perfluoroalkanoic acid and salts thereof from fluorotelomer iodides.
  • the organic additives have electron-donating substituents. Preferred substituents are alkoxy-, alkyl-, alkenyl- , di(alkyl or aryl)amino-, or hydroxy-substituents.
  • Organic additives suitable for use herein include glycols, alkyl alcohols, alkyl ethers, amides, tertiary amines, and salts thereof, and saturated and unsaturated hydrocarbons.
  • the one or more organic additives are present at a level of from about 0.1% to about 20% by weight, preferably from about 0.1 % to about 10%, and more preferably from about 0.1 % to about 5% by weight, based on the weight of the fluorotelomer iodide. Most effective organic additives were found to work at very low loadings, less than about 5% based on the weight of the fluorotelomer iodide.
  • Preferred organic additives have a molecular weight of from about 28 to about 1000.
  • the one or more organic additives are preferably water soluble and/or relatively volatile materials, which after the treatment are easily separated by contacting with an aqueous phase or by evaporation to provide the purified fluorotelomer iodides.
  • organic additives that are easily removed by contacting with an aqueous phase are alcohols, trialkanolamines, such as triethanolamine, or polyalkylether glycols, such as polyethyleneglycols.
  • Examples of organic additives that are easily removed by evaporation are ethylene or propylene.
  • a particularly preferred organic additive is isopropyl alcohol.
  • the resulting purified fluorotelomer iodides are also used to prepare fluorotelomer alcohols and other derivatives.
  • the thermal conditions for the treatment of fluorotelomer iodides are as described above for fluorotelomer alcohols.
  • the thermal treatment is carried out in the presence of one or more organic additives and optional addition of water.
  • the thermal treatment may also include a hydrogen atom donor.
  • the fluorotelomer iodides, singly or in admixture, are heated with the organic additive at above about 175°C, preferably above about 185°C, and more preferably above about 195°C.
  • the upper temperature for the thermal treatment is about 225°C and preferably about 215°C. Above this temperature range the process becomes less economically attractive and undesirable competing reactions can become significant.
  • the purified fluorotelomer alcohols resulting from the process of the present invention are useful for conversion into (meth)acrylate esters, polyurethane polymers, and other derivatives, containing substantially reduced concentrations of the perfluoroalkanoic acids or salts thereof, perfluoroalkanoic acid esters, and perfluoroalkyliodides.
  • the perfluoroalkanoic acids or salts thereof, perfluoroalkanoic acid esters, and perfluoroakyliodides are chemically converted primarily into 1H-perfluoroalkanes.
  • Mixture 1 comprises 1H,1H,2H,2H-perfluoroalkan-1-ols and was obtained from E. I. du Pont de Nemours and Company, Wilmington DE. Designated as Mixture 1 hereafter, the composition by weight is shown in Table 1: Table 1. 1H,1H,2,H,2H-Perfluoroalkan-1-ol Mixture Composition.
  • the parfluorooctanvic acid ester of 2-perfluorooctyl-ethanol was prepared by direct esterification.
  • the quantitative detection (with a detection threshold 1-2 mg/kg) of perfluorooctanoic acid was performed by using a liquid chromatography tandem mass spectrometry method (liquid chromatography/mass spectrometry/mass spectrometry, LC/MS/MS). Standard solutions of perfluorooctanoic acid at known concentrations were run before and after the experimental samples to obtain calibration curve of MS integration area versus sample concentration. The measurement for each experimental sample was also verified by analyzing the sample spiked with the known amount of perfluorooctanoic acid.
  • GC/MS mass selective detector
  • the initial levels of perfluorooctanoic acid and other impurities prior to the treatment were the combination of process impurities and optional spiking of impurities.
  • 1H,1H,2H,2H-perfluorodecan-1-ol (4 g, available from Syn-Quest), spiked with various impurities, ethanolamine (1.5wt.%), and water (10 wt.%), were charged to a 5-mL stainless steel shaker tube, shaken and heated to 200°C for 4 hours. After the separation of aqueous phase, analysis was conducted according to Test Methods 1 and 2.
  • the level of perfluorooctanoic acid had decreased from 311 mg/kg to 12 mg/kg.
  • the level of perfluorooctyl iodide had decreased from 161mg/kg to less than 2 mg/kg.
  • the level of perfluorooctanoic acid ester had decreased from 170 mg/kg to less than 2 mg/kg.
  • a mixture of 1H,1H,2H,2H-perfluoroalkan-1-ols, 450g (Mixture 1, 0.936 mol, average MW 481), ethanolamine (6.75 g, 1.5 wt.%), and water (45 g, 10 wt.%), were charged to a 400-mL stainless steel shaker tube, shaken and heated to 200°C for 4 hours. After the separation of aqueous phase, analyses were conducted according to Test Methods 1 and 2. The level of perfluorooctanoic acid had decreased from 100 mg/kg to 4 mg/kg. The level of perfluorooctyl iodide had decreased from 190 mg/kg to less than 2 mg/kg. The level of perfluorooctanoic acid ester had decreased from 80 mg/kg to less than 2 mg/kg.
  • C 5 F 11 COOH was 5-8 mg/kg
  • C 6 F 13 COOH was less than 4 mg/kg
  • C 8 F 17 COOH and C 9 F 19 COOH were below detection.
  • the level of perfluorooctyl iodide had decreased from 90 mg/kg to less than 2 mg/kg.
  • Titanate A is 80% titanium (IV) (triethasolamineaminato) isopropoxide and 20% isopropyl alcohol, obtained from E. I. du Pont de Nemours and Company, Wilmington DE;

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP09156396.5A 2004-11-05 2005-11-01 Purification d'alcools fluores Active EP2096099B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/983,201 US7138551B2 (en) 2004-11-05 2004-11-05 Purification of fluorinated alcohols
EP05815869A EP1807382B1 (fr) 2004-11-05 2005-11-01 Purification d'alcools fluores

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EP2096099B1 EP2096099B1 (fr) 2016-04-13

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US (1) US7138551B2 (fr)
EP (2) EP2096099B1 (fr)
JP (2) JP4959572B2 (fr)
CN (2) CN101774881B (fr)
HK (1) HK1145083A1 (fr)
TW (1) TWI370114B (fr)
WO (1) WO2006052567A2 (fr)

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KR20100094475A (ko) * 2007-10-26 2010-08-26 이 아이 듀폰 디 네모아 앤드 캄파니 격납된 층을 제조하기 위한 방법 및 재료, 및 이를 사용하여 제조된 소자
US8040048B2 (en) 2007-12-12 2011-10-18 Lang Charles D Process for forming an organic electronic device including an organic device layer
WO2010057691A2 (fr) * 2008-08-11 2010-05-27 Solvay Solexis S.P.A. Hydrofluoroalcools ayant une stabilité thermique et chimique améliorée
JP6794319B2 (ja) * 2017-07-03 2020-12-02 ダイキン工業株式会社 Ｃ８Ｆ１７Ｂｒを含む組成物及びＣ８Ｆ１７Ｂｒの製造方法
US11014999B2 (en) * 2018-04-24 2021-05-25 Inhance Technologies, LLC Systems and methods for processing fluoropolymer materials and related workpieces
CN109297923A (zh) * 2018-09-19 2019-02-01 南通出入境检验检疫局检验检疫综合技术中心 纺织品中微量含氟整理剂的测定方法
JP2019172709A (ja) * 2019-07-17 2019-10-10 ダイキン工業株式会社 Ｃ８Ｆ１７Ｂｒを含む組成物及びＣ８Ｆ１７Ｂｒの製造方法
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EP2096099B1 (fr) 2016-04-13
WO2006052567A2 (fr) 2006-05-18
WO2006052567A3 (fr) 2006-07-27
US7138551B2 (en) 2006-11-21
CN101056835A (zh) 2007-10-17
CN101774881B (zh) 2012-01-18
CN101056835B (zh) 2010-06-16
US20060100464A1 (en) 2006-05-11
JP4959572B2 (ja) 2012-06-27
HK1145083A1 (en) 2011-04-01
JP5442786B2 (ja) 2014-03-12
EP1807382A2 (fr) 2007-07-18
CN101774881A (zh) 2010-07-14
JP2008519079A (ja) 2008-06-05
EP1807382B1 (fr) 2011-12-21
TWI370114B (en) 2012-08-11
JP2012116862A (ja) 2012-06-21

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